CN109806905B - Mercury-free catalyst, preparation method thereof and application thereof in preparation of chloroethylene - Google Patents
Mercury-free catalyst, preparation method thereof and application thereof in preparation of chloroethylene Download PDFInfo
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Abstract
The application discloses a mercury-free catalyst, which is characterized by comprising a carrier and an active component; the carrier comprises an FAU type silicon-aluminum molecular sieve, and the weight percentage of the FAU type silicon-aluminum molecular sieve in the carrier is 50-100 wt%; the active component is CuCl2，CuCl2The weight ratio of the carrier to the carrier is CuCl2: and the carrier is 5-40: 100. The catalyst can be used for acetylene hydrochlorination, and has the advantages of low price, excellent stability and good activity and selectivity; the method avoids the problem of environmental pollution caused by using a highly toxic mercury catalyst, and solves the problem of high cost of the gold catalyst in the current research.
Description
Technical Field
The application relates to a mercury-free catalyst, a preparation method thereof and application thereof in preparation of chloroethylene, and belongs to the field of chemical industry.
Background
Polyvinyl chloride (PVC) is a widely used general-purpose plastic made of vinyl chloride aloneAnd (c) polymerization of the monomer (VCM). The current industrial processes for producing vinyl chloride include mainly ethylene equilibrium oxychlorination and acetylene hydrochlorination. Because of the special energy structure of rich coal, less oil and poor gas in China, the specific gravity of chloroethylene synthesized by coal-based acetylene hydrochlorination in the polyvinyl chloride industry in China is close to 80%, and the industrial catalyst used in the method is an activated carbon-loaded mercuric chloride catalyst (HgCl)2/AC)，HgCl2The volatile property can cause mercury loss of the catalyst, thereby limiting the service life of the catalyst; more serious is HgCl2The toxicity of (2) threatens the safety of the environment and human beings. In 2013, 92 countries and regions sign a water good treaty, production and import and export of mercury-containing products are completely forbidden from the treaty to 2020, and China approves the treaty in 2016. Therefore, the problem of mercury pollution in the acetylene hydrochlorination process is solved, and the development of environment-friendly mercury-free catalysts is urgently needed.
In recent years, many researchers have added to the research of mercury-free catalysts for acetylene hydrochlorination, and the development of mercury-free catalysts has advanced to a certain extent, and noble metal catalysts, especially activated carbon-supported gold catalysts, are considered as the most potential mercury-free catalysts, but are limited by problems such as cost, and no large-scale application has been reported so far. Meanwhile, most acetylene hydrochlorination catalysts select activated carbon as a carrier, and the activated carbon has low mechanical strength and poor regeneration performance.
For this reason, researchers have developed mercury-free catalysts using molecular sieves or metal oxides as supports. The patent CN201010248348.4 discloses a mercury-free catalyst, which takes MCM-41 and other molecular sieves as carriers and takes noble metal ruthenium trichloride as an active component. The patent CN201110257696.2 discloses a mercury-free catalyst, which takes HZSM-5 type, NaZSM-5 type, mordenite, H beta type and HY type molecular sieves as carriers, and halide and complex of noble metal palladium as active components. The patent CN201310124706.4 discloses a mercury-free catalyst, which uses molecular sieve, silica or alumina as carrier, Pt and Cu as main active components, and alkaline earth metal as auxiliary agent.
The non-noble metal has the advantage of low price, and simultaneously has certain acetylene hydrochlorination reaction performance, but the activity, selectivity and stability are not as good as those of noble metal catalysts, and the current research is relatively less. By improving the carrier, the development of the base metal catalyst with low cost and excellent performance undoubtedly has important economic value and strategic significance.
Disclosure of Invention
According to one aspect of the application, a mercury-free catalyst which can be used for acetylene hydrochlorination, is low in price, excellent in stability and good in activity is provided; the mercury-free catalyst avoids the problem of environmental pollution caused by using a highly toxic mercury catalyst, and solves the problem of high cost of the gold catalyst in the current research.
The mercury-free catalyst is characterized in that the catalyst comprises a carrier and an active component;
the carrier comprises an FAU type silicon-aluminum molecular sieve, and the weight percentage of the FAU type silicon-aluminum molecular sieve in the carrier is 50-100 wt%;
the active component is CuCl2，CuCl2The weight ratio of the carrier to the carrier is CuCl2: and the carrier is 5-40: 100.
Preferably, the weight percentage of the FAU-type silicon-aluminum molecular sieve in the carrier is 70-100 wt%. Further preferably, the FAU-type aluminosilicate molecular sieve is present in the carrier in an amount of 100 wt%.
Preferably, CuCl2The weight ratio of the carrier to the carrier is CuCl2: and (3) the carrier is 5-35: 100. Further preferably, CuCl2The weight ratio of the carrier to the carrier is CuCl2: the carrier is 15-25: 100.
The active component CuCl2From anhydrous copper chloride and/or copper chloride dihydrate. Preferably, the active ingredient is CuCl2From copper chloride dihydrate.
As an embodiment, the FAU-type silicoaluminophosphate molecular sieve is a molecular X sieve.
Optionally, the cation in the FAU-type molecular sieve is at least one of hydrogen ion, lithium ion, sodium ion and potassium ion.
Preferably, the FAU type aluminosilicate molecular sieve is a sodium type 13X molecular sieve.
Alternatively, when the carrier contains a binder, the carrier is a shaped carrier. Preferably, the carrier is spherical or clover-shaped.
In one embodiment, the binder is present in the carrier in an amount greater than 0 and equal to or less than 50 wt%. Preferably, the weight percentage of the binder in the carrier is greater than 0 and equal to or less than 30 wt%.
According to a further aspect of the present application, there is provided a method for preparing any of the mercury-free catalysts described above, characterized in that it comprises the following steps:
a) soaking a solution containing copper chloride on a carrier in an equal volume to obtain a precursor I;
b) drying the precursor I obtained in the step a) at 10-30 ℃ for not less than 6 hours to obtain a precursor II;
c) drying the precursor II obtained in the step b) at 100-150 ℃ for not less than 6 hours to obtain a precursor III;
d) and d) placing the precursor III obtained in the step c) in a nitrogen atmosphere for dehydration to obtain the mercury-free catalyst.
Preferably, the solution containing copper chloride in step a) is obtained by dissolving anhydrous copper chloride and/or copper chloride dihydrate in at least one of water and ethanol.
Optionally, the carrier is an FAU type silico-aluminum molecular sieve or a molded carrier containing a binder and an FAU type silico-aluminum molecular sieve.
Preferably, the step b) is to place the precursor I obtained in the step a) at room temperature for airing for 8-20 hours to obtain a precursor II.
Preferably, the precursor II obtained in the step b) is dried for 8-20 hours at 100-150 ℃ to obtain a precursor III in the step c).
Preferably, the dehydration in the nitrogen atmosphere in the step d) is dehydration by nitrogen purging.
According to a particular embodiment, the method for preparing a mercury-free catalyst comprises the following steps: (1) dissolving copper chloride in deionized water or absolute ethyl alcohol; (2) soaking the copper chloride solution on the molecular sieve in equal volume according to the calculated proportion; (3) placing the catalyst prepared in the step (2) at normal temperature and airing; (4) then the catalyst prepared in the step (3) is placed in an oven at the temperature of 100 ℃ and 150 ℃ for drying; (5) and (4) finally, dehydrating the catalyst prepared in the step (4) in a nitrogen atmosphere.
According to still another aspect of the present application, there is provided a method for producing vinyl chloride, characterized in that a raw material gas containing acetylene and hydrogen chloride is passed through a reactor equipped with a mercury-free catalyst to produce vinyl chloride;
the reaction pressure is 0.1MPa, the reaction temperature is 140-240 ℃, and the volume space velocity of acetylene is 30-120 h-1；
The molar ratio of acetylene to hydrogen chloride in the raw material gas is 1: 1.1-1.2;
the mercury-free catalyst is selected from at least one of any mercury-free catalyst described above and a mercury-free catalyst prepared according to any method described above.
Benefits of the present application include, but are not limited to:
(1) the catalyst has high activity, good selectivity and excellent stability in the hydrochlorination reaction of acetylene, the highest conversion rate of acetylene can reach 95 percent, the selectivity of vinyl chloride is higher than 98 percent, and the conversion rate of acetylene and the selectivity of vinyl chloride are basically kept unchanged after the reaction is carried out for more than 100 hours.
(2) The catalyst of the invention has wide temperature range, good stability in the reaction temperature range of 140 ℃ and 240 ℃, and no obvious activity selectivity reduction in the reaction process.
(3) The catalyst of the invention has low cost, the FAU type molecular sieve as the main component of the carrier and the copper chloride as the active component have low price, and the total cost is far lower than that of a gold catalyst.
(4) The catalyst of the invention has simple preparation process and difficult loss of active components.
Drawings
FIG. 1 is sample 1#And sample 2#Reaction results for the preparation of vinyl chloride.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.
EXAMPLE 1 obtaining of vector
13X molecular Sieve (SiO)2/Al2O32.25) raw powder was purchased from austite technologies ltd, Jiangsu.
Na-USY(SiO2/Al2O39.47) from south-opening catalyst plant.
The Li-X molecular sieve is prepared by the following method: adding 1g of 13X molecular sieve into 500mL of 1M lithium nitrate solution, stirring for 2 hours at 60 ℃, performing centrifugal separation, repeatedly exchanging for 2 times, performing centrifugal separation and deionized water washing on the obtained solid for 3 times, and drying for 6 hours at 120 ℃ to obtain the Li-X molecular sieve.
The H-X molecular sieve is prepared by the following method: adding 1g of 13X molecular sieve into 500mL of 1M ammonium nitrate solution, stirring for 2 hours at 60 ℃, performing centrifugal separation, repeatedly exchanging for 2 times, performing centrifugal separation, washing for 3 times by deionized water, drying for 6 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to obtain the H-X molecular sieve.
The K-X molecular sieve is prepared by the following method: adding 1g of 13X molecular sieve into 500mL of 1M potassium nitrate solution, stirring for 2 hours at 60 ℃, performing centrifugal separation, repeatedly exchanging for 2 times, performing centrifugal separation and deionized water washing on the obtained solid for 3 times, and drying for 6 hours at 120 ℃ to obtain the K-X molecular sieve.
Spherical 13X carriers (13X molecular sieve content 75 wt%, binder content 25 wt%), cloverleaf 13X carriers (13X molecular sieve content 50 wt%, binder content 50 wt%), spherical H-X (H-X molecular sieve content 60%, binder content 40 wt%), spherical K-X (K-X molecular sieve content 80%, binder content 20 wt%) were purchased from Jiangsu Austenite science and technology Limited.
Example 2 sample 1#Preparation of
1.50g of anhydrous copper chloride (CuCl) was weighed2) In a beaker, 4.97g of deionized water was added to dissolve and stir well. Weigh 10g of 13X molecular sieve raw powder (SiO)2/Al2O32.25), adding the solution into 13X molecular sieve raw powder, uniformly stirring, airing at room temperature for 12h, drying at 100 ℃ for 12h, then drying under nitrogen purging for 1h to obtain the mercury-free catalyst with the copper chloride loading of 15%, and marking as a sample 1#。
Example 3 sample 2#Preparation of
3.17g of copper chloride dihydrate (CuCl) were weighed2.2H2O) is put into a beaker, and 4.73g of absolute ethyl alcohol is added to dissolve and stir evenly. Weighing 10g of 13X molecular sieve raw powder, adding the solution into the 13X molecular sieve raw powder, uniformly stirring, airing at room temperature for 12h, drying at 120 ℃ for 12h, then drying under nitrogen purging for 1h to obtain a mercury-free catalyst with copper chloride loading of 25%, and marking as a sample 2#。
Example 4 sample 3#～17#Preparation of
The preparation process and the raw material ratio are the same as those of the sample 1 in the example 1#The difference in the preparation of (1) is that the raw materials, the mixture ratio and the preparation conditions were changed, and the relationships between the sample numbers and the raw materials, the mixture ratio and the preparation conditions are shown in table 1.
TABLE 1
Example 5 reaction Performance measurement
Respectively mixing the samples 1#～17#The catalyst is used for acetylene hydrochlorination, and comprises the following specific steps:
the sample was packed into a tubular fixed bed reactor (diameter 10mm, height 300mm), and before the reaction, moisture and air in the system were purged by introducing nitrogen and the temperature was raised to a specific reaction temperature. After the temperature is stable, the raw material gas is introduced into the reactor through a mass flow meter according to the molar ratio of acetylene to hydrogen chloride of 1.2: 1. The product at the outlet of the reactor passes through a cold well and a dryer and then is introduced into a gas chromatography for analyzing the composition.
Sample 1 was added#Is used for acetylene hydrochlorination reaction at an acetylene airspeed of 60h-1At a reaction temperature of 200 ℃, the initial acetylene conversionThe conversion rate is 55 percent, the selectivity of vinyl chloride is 98.8 percent, and the activity and the selectivity are continuously increased after 50 hours of reaction (see figure 1).
Sample 2 was added#Is used for acetylene hydrochlorination reaction at an acetylene airspeed of 30h-1When the reaction temperature is 220 ℃, the acetylene conversion rate is 95%, the vinyl chloride selectivity is 99.0%, and the activity and the selectivity are basically kept unchanged after 100 hours of reaction (see figure 1).
Sample 3#～17#The reaction conditions and the reaction results are shown in table 2.
TABLE 2
aAcetylene conversion (1-molar concentration of acetylene at reactor outlet/(molar concentration of acetylene at reactor outlet + molar concentration of product at reactor outlet)) × 100%, which is the sum of the molar concentrations of the substances other than acetylene at the outlet.
bSelectivity to vinyl chloride was × 100% molar concentration of vinyl chloride at the reactor outlet/molar concentration of product at the reactor outlet.
cThe catalyst life is: reaction time at which acetylene conversion dropped to 95% of maximum conversion.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (15)
1. A mercury-free catalyst, characterized in that the catalyst comprises a support and an active component;
the carrier comprises an FAU type silicon-aluminum molecular sieve, and the weight percentage of the FAU type silicon-aluminum molecular sieve in the carrier is 50-100 wt%;
the active component comprises CuCl2，CuCl2The weight ratio of the carrier to the carrier is CuCl2: and the carrier is 5-40: 100.
2. The mercury-free catalyst of claim 1, wherein the FAU-type aluminosilicate molecular sieve is present in the carrier in an amount of 70 to 100 wt%.
3. The mercury-free catalyst of claim 1, wherein the FAU-type aluminosilicate molecular sieve is present in the support in an amount of 100 wt%.
4. The mercury-free catalyst of claim 1, wherein the CuCl is2The weight ratio of the carrier to the carrier is CuCl2: and (3) the carrier is 5-35: 100.
5. The mercury-free catalyst of claim 1, wherein the CuCl is2The weight ratio of the carrier to the carrier is CuCl2: the carrier is 15-25: 100.
6. The mercury-free catalyst of claim 1, wherein the FAU-type silico-aluminum molecular sieves are X-type molecular sieves and/or Y-type molecular sieves.
7. The mercury-free catalyst of claim 6, wherein the cation in the FAU-type molecular sieve is at least one of a hydrogen ion, a lithium ion, a sodium ion, and a potassium ion.
8. The mercury-free catalyst of claim 6, wherein the FAU-type aluminosilicate molecular sieves are sodium-type 13X molecular sieves.
9. The mercury-free catalyst of claim 1, wherein the support comprises a binder.
10. A method for preparing a mercury-free catalyst according to any of claims 1 to 9, characterized in that it comprises the following steps:
a) soaking a solution containing copper chloride on a carrier in an equal volume to obtain a precursor I;
b) drying the precursor I obtained in the step a) at 10-30 ℃ for not less than 6 hours to obtain a precursor II;
c) drying the precursor II obtained in the step b) at 100-150 ℃ for not less than 6 hours to obtain a precursor III;
d) and d) placing the precursor III obtained in the step c) in a nitrogen atmosphere for dehydration to obtain the mercury-free catalyst.
11. The method according to claim 10, wherein the solution containing copper chloride in step a) is obtained by dissolving anhydrous copper chloride and/or copper chloride dihydrate in at least one of water and ethanol; the carrier is an FAU type silicon-aluminum molecular sieve or a molding carrier containing a binder and the FAU type silicon-aluminum molecular sieve.
12. The method according to claim 10, wherein the step b) is to air-dry the precursor I obtained in the step a) at room temperature for 8-20 hours to obtain a precursor II.
13. The method according to claim 10, wherein the precursor II obtained in step b) is dried at 100-150 ℃ for 8-20 hours to obtain the precursor III in step c).
14. The method of claim 10, wherein the step d) of dehydrating in a nitrogen atmosphere is dehydrating by purging with nitrogen.
15. A method for preparing chloroethylene is characterized in that raw material gas containing acetylene and hydrogen chloride is passed through a reactor filled with a mercury-free catalyst to prepare chloroethylene;
the reaction pressure is 0.1MPa, the reaction temperature is 140-240 ℃, and the volume space velocity of acetylene is 30-120 h-1；
The molar ratio of acetylene to hydrogen chloride in the raw material gas is 1: 1.1-1.2;
the mercury-free catalyst is selected from at least one of the mercury-free catalyst according to any one of claims 1 to 9 and the mercury-free catalyst prepared by the method according to any one of claims 10 to 14.
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